540 Chemie und zugeordnete Wissenschaften
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Synthese neuer organischer Schwefelverbindungen aus aromatischen Thiolverbindungen und Sulphinsäuren
(2001)
Die rasche Entwicklung der Chemie organischer Schwefelverbindungen in der zweiten Hälfte des 20. Jahrhunderts wurde durch drei wichtige Prozesse ausgelöst:
- die Einbeziehung von schwefelhaltigen und stark schwefelhaltigen Erdölen sowie die Verwendung von schwefelhaltigen Abfällen zur Steigerung der Produktion, die durch die Entwicklung anderer Industriebranchen notwendig wurde;
- die Erweiterung der Anwendungsbereiche von organischen Schwefelverbindungen bei der Produktion von Arzneimitteln, Pestiziden, Flotationsmitteln, Zusatzstoffen für Öle und Heizstoffe, Inhibitoren gegen Metallkorrosion, Polymerisationsreglern, Farbstoffen u. a.;
- durch das große Interesse an organischen Schwefelverbindungen als Modelle für die Erforschung vieler wichtiger Grundlagenkonzeptionen in der organischen Chemie.
Aus diesem Grunde ist die Synthese neuer organischer Schwefelverbindungen mit potenziell nützlichen Eigenschaften sowie die Untersuchung der Gesetzmäßigkeiten des Reaktionsverlaufs mit dem Ziel, diese Prozesse bewusst zu steuern, von besonderer Aktualität. In der vorliegenden Arbeit wurden Reaktionen der nukleophilen Addition von aromatischen Thiolverbindungen und Sulfinsäuren an aktivierte Doppelbindungen (Vinylketone und Akrylnitrile) und die weitere Umwandlung der entstandenen Addukte zu heterozyklischen Verbindungen untersucht.
Several mutation positions have been chosen for introducing positively charged lysines in human cytochrome c (cyt c) with the aim of increasing the reaction rate with superoxide radicals (SO) and thus, the sensitivity of an electrochemical cyt c based SO biosensor. The impact of the mutations on structural and redox properties as well as on the reaction rate with SO are verified. Four mutants show a higher reaction rate with the radical compared to the wild type. These mutants are used for the construction of SO sensors based on thiol-modified gold electrodes and covalently fixed proteins. The E66K mutant electrode has a clearly higher sensitivity in comparison to the wildtype based sensor.
Shape memory polyurethanes (SMPUs) were synthesized by 4,4′-diphenylmethane diisocyanate (MDI), hexane-1,6-diol (HD), polypropylene glycol (PPG), and recycled polyvinyl butyral (PVB). Dynamic mechanical analysis, differential scanning calorimetry and Fourier transformation infrared attenuated total reflection spectroscopy was used to characterize the poly (vinylbutyral-urethanes). Micro-phase domain separation of hard and soft segments and phase inversion were investigated. Increasing the hard segment content, i.e., average hard segment molecular weight, leads to an increase in the degree of micro-phase separation, hard domain order and crystallinity. The crystalline hard segment structures combined with the elastic nature of soft segment matrix provide enough physical and chemical crosslinks to have shape memory effect.
The sample preparation for biological and chemical probes involves following a strict workflow to eliminate any contamination to the sample beforehand. Furthermore, it is time consuming and must be carried out by trained personnel such as a nurse or other supervisors, making it therefore expensive. The development of novel sample preparation techniques paired with modern sample analysis systems is focused on improving the operability while keeping a constant quality of results. This is important to analyse samples, which cannot be determined with current screening conditions. The analysis of analytes is required to receive a more detailed picture of the patient and to fully understand its complexity. Possible samples for in-depth analysis of chemical origin can be cholesterol or glucose. More complex samples, such as blood or saliva, require a sophisticated system, which analyses the samples for their individual compounds.
Es wurde ein chemisches Recyclingverfahren für PUR entwickelt, welches durch Einsatz eines Extruders und in Tandemfahrweise betriebener Nachreaktionsbehälter kontinuierlich gestaltet wurde. In Nebenreaktionen entstandene primäre aromatische Amine werden in einer synchron zur Hauptreaktion verlaufenden Umsetzung in stickstoffhaltige Polyole umgewandelt. Die chemischen und anwendungstechnischen Eigenschaften der nach diesem Verfahren hergestellten Recyclatpolyole werden dargestellt. Diese Polyole sind zur Formulierung harter, halbharter und zähharter zelliger und nichtzelliger PUR geeignet. Die Betrachtung ökonomischer und ökologischer Gesichtspunkte schließt die Arbeit ab.
The synthesis of polyurea dispersion polyols (PHD) was developed using a new route via depolymerization of polyurethane polyureas by a mixture of at least two glycols in the presence of a consumable catalyst, i. e. a secondary aliphatic amine. On this way such polyols were produced with a particle size distribution with a maximum in the 120 to 400 nanometer region with hydroxyl numbers of 180 to 300 mg KOH/g being optically clear and highly reactive. The exact adjustment of the ethylene oxide content of the reaction mixture together with that of the polyether polyol originally present in the polyurethane polyurea used in a predetermined range of surface tension as well as specific reaction conditions leads to these polyols which will give in turn polyurethanes with exceptional properties.
Methylcellulose (MC) / SiO2 organic / inorganic hybrid materials have been prepared from MC and methyltriethoxysilane or ethyltrimethoxysilane, and characterized by XRD, FTIR and AFM. XRD showed peak shifts. FTIR shows intermolecular hydrogen bonding between MC and SiO2. AFM depicts surface roughness which depends on the silica precursor and MC content.
Nanostructured ferritic oxide dispersion strengthened (ODS) alloy is an ideal candidate for fission/fusion power plant materials, particularly in the use of a first-wall and blanket structure of a next generation reactor. These steels usually contain a high density of Y-Al-O nanoparticles, high dislocation densities and fine grains. The material contains nanoparticles with an average diameter of 21 nm. Irradiation of these alloys was performed with a dual beam irradiation of 2.5 MeV Fe+/31 dpa and 350 keV He+/18 appm/dpa. Irradiation causes atomic displacements resulting in vacancy and self-interstitial lattice defects and dislocation loops. Additionally to structural changes, the effect of the irradiation generated defects on the mechanical properties of the ODS is investigated by nanoindentation. A clear hardness increase in the irradiated area is observed, which reaches a maximum at a close surface region. This feature is attributed to synergistic effects between the displacement damage and He implantation resulting in He filled vacancies
The redox behavior of proteins plays a crucial part in the design of bioelectronic systems. We have demonstrated several functional systems exploiting the electron exchange properties of the redox protein cytochrome c (cyt c) in combination with enzymes and photoactive proteins. The operation is based on an effective reaction at modified electrodes but also to a large extent on the capability of self-exchange between cyt c molecules in a surface-fixed state. In this context, different variants of human cyt c have been examined here with respect to an altered heterogeneous electron transfer (ET) rate in a monolayer on electrodes as well as an enhanced self-exchange rate while being incorporated in multilayer architectures. For this purpose, mutants of the wild-type (WT) protein have been prepared to change the chemical nature of the surface contact area near the heme edge. The structural integrity of the variants has been verified by NMR and UV–vis measurements. It is shown that the single-point mutations can significantly influence the heterogeneous ET rate at thiol-modified gold electrodes and that electroactive protein/silica nanoparticle multilayers can be constructed with all forms of human cyt c prepared. The kinetic behavior of electron exchange for the mutant proteins in comparison with that of the WT has been found altered in some multilayer arrangements. Higher self-exchange rates have been found for K79A. The results demonstrate that the position of the introduced change in the charge situation of cyt c has a profound influence on the exchange behavior. In addition, the behavior of the cyt c variants in assembled multilayers is found to be rather similar to the situation of cyt c self-exchange in solution verified by NMR.